Synergistic insecticidal compositions



compositions of enhanced killing power.

United States Patent M SYNERGlS'I-IC INSECTICIDAL COMPOSITIONS Howard A. Jones and John A. Garman, Baltimore, Md., and Berton C. Dickinson, Lyndonville, N.Y., assignors to Food Machinery and Chemical Corporation, New York, N.Y., a corporation ofDelaware No Drawing. Original application Mar. 24,1955, Ser. No. 496,596. Divided and this application Oct. 15, V 1958, Ser. No. 767,255 V 12 Claims. (Cl. 167-22) ticularly, this inventionrelates to synergistic insecticidal compositions of these-compounds wherein the insecticidal eifectivenessof each component is enhanced by the presenceof the other to produce an unexpected combined effect.

activity, the resulting 'phenomenon is called synergism;

. The mechanism of synergism is by no means understood.

It is, in fact, quite probable that it diifers with different I synergistic combinations. The term. fs ynergism? can be defined, however, as aecooperative aetion yvhich is en-. :countered in combinationsof two or more biologically active components inwhich the combined activity of the two components exceeds the sum of. the activities of the components when used alone. The insecticidal activity of the mixedcomponents cannot be predictedfrom known values of the individualcomponents, but is unpredictable and depends on the individual activity of neither.

It is anobject of this invention to; provide insecticidal Another object of this inven tionis toproduce novel compositions containing compounds capable of synergizing the knockdown andjkillingfproperties of individual toxicants. A

further object of this invention is to provide compositions including a relatively toxic phosphorous containing insecticide in which superior insecticidal activity is obtained because of the synergistic eifects, but in which the ultimate toxicity to Warm-blooded animals is greatly reduced be-' When two or'more substance s in combination show an. unexpectedly. high activity, as for. instance,.insecticidal 2,945,780 ,Patented July 19, ,1960

Mexican bean beetle. The combinations are highly effective and economical to use for such large-scale insecticidal requirements as the control of truck crop, forage crop and orchard insects. h

The synergistic compositions of this invention can be formulated as aqueous emulsions, as dry or wettable powders, as solutions or in any other suitable vehicle. The insecticidal compositions can be utilized as sprays, as dusts, as aerosol mixtures, insecticidal coating compositions, and as residues. In general, they can be applied by methods commonly used for control or eradication of insects, mites and thelike. Thus these insecticidal compositions can be formulated with solvents, diluents and carrier media, adhesives, spreading, wetting per 40 parts of the latter and preferably about 1 part of the former to about 2 parts of the latter.

The quantities of the component toxicants in the final insecticidal compositions can range from 0.01% to 25.00% for the Malathionhandifrom 0.05% to 50.00%

cause of the' lower concentrationsof the phosphorous compounds required when usedin combination with the relatively less toxic carbamates. Other objects and advantages of the invention will become apparent from the description of'the invention set forth below.

According to this invention there are provided synergistic .insecticidal compositions comprising 0,0-dimethyl S-(1,2-dicarbethoxyethyl) 1 dithiophosphate,'- hereinafter called Malathion, and an organic carbamate ester of the following general formula The synergistic insecticidal compositions ofthis invention may be used one wide variety of insect and mite species, but are particularly effective against such insects as the two-spotted spider mite, harlequin bug and for-the carbamate, and preferably from 0.10% to 10.00% forlthe Malathion and from 0.10% to 25.00% for the carbarnate.

The procedures of the testing methods are described below. The details of the test experiments including the a type of formulation and .mode of application or dosing,

and the species of insects which served as test subjects are given in'the examples.

Insects used in the testing included the house fly (Musca domestica L.), Mexican bean beetle (Epilachna variv estis Muls.), pea aphid (Macnosiphum pisz'. [Kltb.] two-spotted spider mite (Tetranychus bimaculatus Harvey), harlequin bug (Murgan tia histrionica [Hahn]), andsquash bug (Anasa tristz's).

The test methods used are described as follows:

DUST TOWER, "METHOD This general method is described in the following reference, Moore, J. Econ. But. 43, No. 2, 188-190 (1950). 1

The dusting apparatus consists of a vertical glass cylinder, 34 inches high and 8.5 inches in diameter, into which the appropriate dust sample is discharged through a smallhole in the center of the cover, by means of a small laboratory duster operating at an air pressure of 40 p.s.i.g. The duster assembly comprises a 10 m1. beaker, into which the weighed sample is placed, and fitted with a rubber stopper through which pass the air inlet and dust outlet tubes, both of which are made of 4 inch .diameter'copper tubing. At the outer end of theair drilled at irregular intervals which serve as air inlets.

Such an arrangement causes pronounced turbulence of the dust and thus insures exhausting the complete sample from the beaker. The dust outlet tube forms an arch :from the top of-the beaker to the top of the glass dusting tower. h After discharge of the sample into the tower, there is allowed a 2-minute settling time before removal of foliage amount of dust deposited on it, it is then possible to calculate the amount applied per acre.

Each

Table 1 in the field and the cut ends of the stem were wrapped in moist cotton. Individual leaves were then placed in 3.5 inch Petri dishes and dusted as described above. treated leaf was then infested with 10 last instar squash replaced. At the end of '24 hours the treated leaves were removed and fresh untreated leaves were introduced into the dishes. Mortality counts were taken after the bugs had been on the untreated leaves for 24 hours.

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Slight modificationsin'this test employed for specific 5 bug nymphs and the covers of the Petri dishes were insect species are as noted below.

Mexican bean beetle.-In tests using this insect, bean foliage was dusted then infested with fourth instar Mexican bean beetle larvae.

comprising 0,0-dimethyl S-( 1,2-dicarbethoxyethyl) dithiophosphate, and an organic carbarnate ester of the following general formula The results of'the data summarized in Table 1 demonstrate the marked synergism of the insecticidal composimite.-In tests on two-spotted tions of this invention on a number of insects. mites, the mites were confined to the upper surfaces of This application is a division of copending application potted bean'plants y a efoot ring; Thebean Serial No. 496,596, filed March 24, 1955, now abandoned, plants were placed in the glass tower and the mites diwhi h i a continuation-in-part of Serial No. 427,374,

filed May 3, 1954, now abandoned.

We claim: 1. Synergistic insecticidal compositions Mortality readings were taken at Mortality counts were taken in NCOO- 24 hours, then treated foliage was replaced with 1111- 60 treated. Mortality records were made at 48 hours.

Two-spotted spider rect-dusted. Mortality readings were taken in 24 hours. Only adult mites were used in, determining mortality counts.

Pea aphid.Pea plants were infested with pea aphids and fdirect-dusted.

24 hours. 7

Harlequin bug.--The foliage was dusted, then infested with harlequin bugs. 24 hours.

Squash bug.-For this test squash leaves were collected wherein R is selected from the group consisting of ethyl, isopropyl, butyl, n-butyl, tert-butyl and dodecyl radicals, and wherein said components are present in the ratio of about two parts of said carbamate per part of said dithiophosphate.

2. The method of killing insects which comprises applying to the insects and their habitat a synergistic insecticidal composition comprising 0,0-dimethyl S-(1,2-dicarbethoxyethyl) dithiophosphate, and an organic carbamate ester of the following general formula wherein R is selected from the group consisting of ethyl, isopropyl, butyl, n-bu-tyl, tert-butyl and dodecyl radicals, and wherein said components are present in the ratio of about two parts of said carbamate per part of said dithiophosphate.

3. Synergistic insecticidal compositions comprising 0,0-dimethyl S-(1,2-dicarbethoxyethy1) dithiophosphate and phenyl -N-ethyl carbamate.

4. A composition according to claim 3 wherein said components are employed in the ratio of about 2 parts of 0,0-dimethyl S-(l,2-dicarbethoxyethyl) dithiophosphate and phenyl N-n-butyl carbamate.

8. A composition according to claim 7 wherein said components are employed in the ratio of from about 2 parts of carbamate ester to about 1 part of said dithiophosphate.

9. Synergistic insecticidal compositions comprising 0,0-dimethyl S-(1,2-dicarbethoxyethyl) dithiophosphate and phenyl N-tert-butyl carbamate.

10. A composition according to claim 9 wherein said components are employed in the ratio of about 2 parts of said carbamate ester to about 1 part of said di-thiophosphate.

11. Synergistic insecticidal compositions comprising the 0,0d.imethyl S-(LZ-dicaIbethoXyethyI) dithiophosphate and phenyl N-dodecyl carbamate.

12. A composition according to claim 11 wherein said components are employed in 'a ratio of about 2 parts of said carbamate ester to about 1 part of said dithiophosphate.

References Cited in the file of'this patent UNITED STATES PATENTS Jelinek Apr. 11, 1950 Gysin May 25, 1954 OTHER REFERENCES 

2. THE METHOD OF KILLING INSECTS WHICH COMPRISES APPLYING TO THE INSECTS AND THEIR HABITAT A SYNEGISTIC INSECTICIDAL COMPOSITION COMPRISING O,O-DIMETHYL S-(1,2-DICARBETHOXYETHYL)DITHIOPHOSPHATE, AND AN ORGANIC CARBAMATE ESTER OF THE FOLLOWING GENERAL FORMULA 